J. Phys.: Condens. Matter 12 (2000) A459A463.

Printed in the UK

PII: S0953-8984(00)06909-5

Critical behaviour of complex systems

Ramon G Rubio and Francisco Ortega
Departamento de Qumica Fsica I, Facultad de Qumica, Universidad Complutense,
28040-Madrid, Spain
Received 12 August 1999
Abstract. An overview of recent results of the critical behaviour of micellar systems is given.
It is found that it is possible to define a master curve for the effective critical exponent eff for
systems that show a monotonic crossover. It is also shown that the critical behaviour of the osmotic
susceptibility of a metastable critical system is the same as that of stable systems. Finally the
two-exponential decay of the fluctuations of the order parameter is discussed.

1. Introduction
The range of universal critical behaviour in complex fluids (micelles, polymers, ionic fluids
etc) is so small that it may not be experimentally accessible. In some cases, they exhibit a
complex non-monotonic crossover from Ising to mean field behaviour [1]. Due to the limited
extent of the asymptotic (Ising) regime, understanding the thermodynamic behaviour in the
crossover region is extremely relevant from an experimental point of view in order to avoid
puzzling results with respect to the experimental values of the critical exponents [2].
Ionic micellar systems are interesting since depending on the salt content their phase
diagram may present an intersection between a critical line and a surface of first order phase
transitions [3]. On one hand, this makes them useful for testing some of the theoretical
predictions for systems near a critical end point (CEP) [4]. On the other hand, in driving the
system below the CEP, they offer the possibility of studying the critical behaviour of systems
in a metastable state.
In recent years, it has been found that for some systems the decay of the order parameter
fluctuations is more complex than for simple fluids [57]. Although such a behaviour was
already predicted by the asymmetric H model many years ago [8], two-exponential correlation
functions had only been reported for a mixture near its vapourliquid critical line [9].
In this work we will report some experimental results for an ionic micellar system:
dodecylammonium chloride (DAC) + water + KCl. Since the salt content is the same in
the two coexisting phases, the system can be considered as pseudobinary. The system shows
an upper critical solution temperature. At low values of [KCl] the critical line intercepts the
Krafft line, i.e. the line at which the a solid phase of pure surfactant is in equilibrium with the
liquid.
In section 2 we will discuss the behaviour of the order parameter for three different values
of [KCl], and compare it with other systems previously measured. In section 3 we present the
results of the osmotic compressibility for a metastable critical sample. Finally, in section 4
we comment on the decay of the order parameter fluctuations for the same sample.
Corresponding author.
0953-8984/00/SA0459+05$30.00

2000 IOP Publishing Ltd

A459

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R G Rubio and F Ortega

2. Coexistence curves and order parameter

We have obtained detailed coexistence curve data for the poly(oxymethylene) (C7 E5 ) + water
and the DAC + water + KCl system at the three values of [KCl]/M: 0.305, 0.280, 0.265. The
order parameter is well described by the Wegner expansion [10]:
w = B0 t (1 + B1 t  + B2 t 2 + )

(1)

where = 0.325 0.001 and  = 0.51 0.02 are critical exponents; t = (T Tc )/Tc ;
and the Bi are critical amplitudes. Both in the C7 E5 and the DAC systems, the range of
validity of the simple scaling is small (t < 104 ) when compared to mixtures of simple fluids
[10]. In the DAC systems this range decreases as the CEP is approached. Also, for the above
systems B1 > 0, which means that the effective exponent eff = d log(w)/ d log t presents a
monotonic crossover from the Ising value ( = 0.325) to the mean-field value ( = 0.5) upon
increasing t [1]. According to Fisher [2] and Bagnuls and Bervillier [11], the crossover will
depend upon the internal scale length  characteristic of each system. As a consequence, it
should be possible to define a universal crossover curve eff against tr , where tr = tat , where
at is related to  [11]. Figure 1 shows the crossover master curve for eff for the micellar
systems studied in this work, and for other systems previously studied and for which B1 > 0.
We have considered at = 1 for the methanol + n-heptane system since eff 0.325 over the
whole experimental range. In order to make a more strict test of this theoretical prediction, we
have included in figure 2 the systems polystyrene + acetone and 2-butanol + water which are
not too far from a double critical point. In these two cases the field t is defined according to
Malomuzh and Veytsman [12]. The quality of the crossover curve is very good. When values
of eff for some ionic fluids are considered they deviate from the master curve. This reflects
the need of using two crossover parameters for each system, as pointed out by Anisimov et al
[1].

Figure 1. Master curve for the effective critical exponent of the order parameter in different systems.
The shift factor aT has been calculated with respect to the methanol + n-heptane system. The field t
for the systems polystyrene + acetone and 2-butanol + water has been calculated according to [12].

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Figure 2. Universal crossover function for the reduced susceptibility 0 as a function of the
reduced temperature = t/Gi. The dashed line represents the mean-field (MF) behaviour. The
empty squares correspond to the DAC + water + KCl system at the four values of [KCl] studied
in this work. The crosses, circles and full triangles correspond to the microemulsion of Seto et al
[15].

3. Static critical behaviour of a micellar system in a metastable state

In previous works we have studied the correlation length and the osmotic compressibility
for the DAC system with the three values of [KCl] mentioned above [13]. It is possible to
undercool the system below the Krafft line, which opens the possibility of exploring the critical
behaviour of a metastable system. In this work, we have chosen the value [KCl] = 0.205 M.
From the q and T dependences of the intensity of the scattered light, we have obtained
the critical exponents associated with , and associated with . As for the systems above
the Krafft line, their values agree with the Ising ones within the experimental error when one
correction term is used in the Wegner expansion. As in the case of the coexistence curves, the
amplitude of the first correction term is positive, thus one may expect a monotonic crossover
from the Ising to the mean-field values of and . Also, the range of validity of simple scaling
for and is almost one order of magnitude larger than for the order parameter.
Belyakov and Kiselev have proposed a phenomenological extension of the crossover
process as described by the -expansion theory [14]. They arrived at the following expression
for the susceptibility
/ ( 1)/

= (1 + 2.3330
= t/Gi

0 = a0 Gi

/ /

[01 + (1.23330

]
(2)

where a0 is related to the bare mass term of the free energy, and Gi is the Ginzburg number.
As observed in figure 2, equation (2) is able to describe the susceptibility data of the DAC
systems for the four salt concentrations considered in the present work. Figure 2 also includes
the results of Seto et al for a three-component microemulsion [15]. The present set of results
covers the whole crossover region from the asymptotic Ising region ( < 1) to the mean-field
one ( > 300), and points out that the critical metastable system behaves like the stable ones.
Similar conclusions can be drawn from the data.

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R G Rubio and F Ortega

4. Two-exponential decay of dynamic light scattering

In a previous work [7] we found that the intensity correlation functions obtained for the
DAC + water + KCl systems could not be described by a single exponential decay except
far from the critical temperature. We have carried out a similar study for the metastable system
with [KCl] = 0.205 M. Figure 3 shows that the relaxation time distributions are monomodal
far from Tc , while they are bimodal near the critical point. The mode corresponding to smaller
(fast mode) presents a diffusive (q 2 ) behaviour, and there is a smooth continuity with the
single mode found far from Tc . The behaviour of the diffusion coefficient corresponding to
the fast mode Df = f /q 2 (f being the decay rate characteristic of the fast mode) for the
metastable sample was found to be the same as for other samples above the Krafft temperature.
In contrast, for the slow mode s shows a crossover from a q 2 to a q 3 dependence, as shown
in figure 4. Since for this system Gi = 6 105 , all the data shown in figure 4 are in the
crossover and MF regimes (see figure 3).

Figure 3. Relaxation time distribution functions for the metastable system DAC + water + KCl
(0.205 M) corresponding to a scattering angle of 90 and for different values of T = |T Tc |.

In order to obtain the critical Dc and background Du contributions from f and s we

have followed the same method as in [7]. The results lead to two main conclusions: first,
the two modes are essentially decoupled, thus the fast mode contains mainly the background
contribution to the diffusion coefficient, and the slow mode the critical contribution. Second,

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A463

Figure 4. Temperature and wavevector (q) dependence of the decay rate of the slow-relaxation
mode (slow ) for the metastable system with [KCl] = 0.205 M. Notice the crossover from a q 2 to
a q 3 regime. T = |T Tc |.

the critical reduced diffusion coefficient is well described by the Kawasaki function derived
from the mode coupling theory. This is in agreement with recent predictions of Anisimov et al
[16], and with the findings for the DAC systems above the Krafft line [10].
Acknowledgments
This work was supported in part by DGES under grant 96/609 and by Fundacion Ramon
Areces.
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[4]
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[8]
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[10]
[11]
[12]
[13]
[14]
[15]
[16]

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